CN104981933B - Redox flow battery system and the method for controlling it - Google Patents

Redox flow battery system and the method for controlling it Download PDF

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Publication number
CN104981933B
CN104981933B CN201280077730.0A CN201280077730A CN104981933B CN 104981933 B CN104981933 B CN 104981933B CN 201280077730 A CN201280077730 A CN 201280077730A CN 104981933 B CN104981933 B CN 104981933B
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electrode
monopolar cell
cell pile
battery
electrolyte solution
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CN104981933A (en
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普拉西多·玛利亚·斯帕齐安特
迈克尔·蒂山德
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HYDRAREDOX TECHNOLOGIES Inc
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HYDRAREDOX TECHNOLOGIES Inc
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    • Y02E60/30—Hydrogen technology
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Abstract

A kind of new many battery pile frameworks, allow the deployment of the simple electro-kinetic instrument instrument of data acquisition/monitoring of crucial hydraulics, electricity and electrochemistry amount with special characteristic, based on this, the key message of depth and enhanced reliability can be collected/handled to operator or electronic controller, any battery of " restraining oneself state " is in for immediately determining that, and most it excludes from system and possibly replaces it with idle battery at last.A kind of method of the operation of monitoring/control vanadium redox battery system is also disclosed.

Description

Redox flow battery system and the method for controlling it
Technical field
This disclosure relates to which the redox flow battery system for energy stores, the system is used by serial " press filtration " group Many cell electrochemical reaction devices of plane component composition are filled to form battery pile, and for monitoring each of many battery piles The method of the work of the operating condition of electrode and each electrode of many battery piles of control.
Background technology
As effective energy conserving system, redox flow battery system increasingly receives much attention.In numerous oxidations also It is former in candidate, whole vanadium oxide reduction system is one of most preferably.
The electrochemical reactor for redox flow battery system is proposed, it is general to be derived from structure The electrochemical reactor structure that electrolytic process is developed, what only adaptability considered is on the material as electrode.
Document GB-A-2,030,349, US-A-4,786,567, WO99/39397, WO01/03213, WO01/03224, WO01/76000, WO02/15317, WO03/003483, WO03/007464, WO03/043170, WO2004/079849, EPRI, Technical Update Report, " Vanadium Redox Flow Batteries " (An In-depth Analysis),Company of-2007-Electric Power Research Institute, US-2012/0156535-A1, WO2012/001446, WO2012/ 020277, WO2012/032368, WO2012/042288 and especially article " State of charge monitoring Methods for vanadium redox flow battery control ", Maria Skyllas-Kazacos, Michael Kazacos, Australia, New South Wales 2052, Sydney, chemical engineering institute of University of New South Wales, energy magazine (Journal of Power Sources)：196 (2011) 8822-8827, to state of art provide sufficiently comment with And provide discussion to the specific apparatus of the control of vanadium redox system.
Typically, in oxidation, reduction liquid storage system, except not considering the gas (H under correct operating condition2、O2 Or other elements) discharge at electrode, except the minority that must definitely prevent or occur with very little degree is unexpected Parasitics, electrode itself is that chemical lazyness (is not involved in any change at the surface that they are infiltrated by electrolyte solution Property).These conditions cause the ion that oxidation-reduction process is supported to the material transmission in active electrode site and influenceed in electrification Learn the electrochemistry and physics on the infiltration surface of the electrode material for the power that the ionic redox at each electrode of battery is acted on Feature turns into the parameter of most critical together.For many in these systems, such as full vanadium (V/V) redox flow Galvanic battery system and similar system (Fe/V, V/Br, Cr/Fe, Zn/Ce, polysulfide/Br), in order to support economically to be subjected to Current density, porous and fluid permeable electrode is required.
In addition, during the charging and discharging cycle of redox storage system, when from cathodic polarization to anode pole Change when changing, it is necessary to which the chemical inertness of holding electrode material, when being polarized on electrolyte solution positive pole, it is necessary to have relatively high H+ electric discharge overvoltage, and when polarize on electrolyte solution negative pole it is necessary to have relatively high OH- electric discharges overvoltage, So that carbon-based electrode must be used.
Typical pile cell component considers the impermeable ion permeable membrane battery separators of liquid, in membrane separator Identical on both sides is porous and fluid permeable carbon felt electrode makes electrical contact with each carbon-based electrical conductance backboard, with non-conductive frame Frame (generally by plastic manufacturing) limits each liquid flow chamber of positive electrolyte solution and negative electrolyte solutions respectively together.
It is conductive according to the common framework mode of the bipolar pile of electrically coupled in series multiple batteries between two terminal components Backboard usually from battery inner separator element.According to alternative framework mode (WO2004/079849), many battery pile components Conductive backings separation staggeredly multiple same-signs liquid flow chamber, the double-sided electrode electrically connected parallel.
To electrode material transmission must by the forced fluid flow of two kinds of electrolyte solutions via each porous electrode room Lai Auxiliary.Certainly, pumping electrolyte solution represents " Passive Power ", and " Passive Power " greatly detracts each complete of energy stores The general power yield in cycle.
Generally, due to which memory capacity is not directly limited to electrochemical reactor by oxidation, reduction liquid storage system Size property, the large storage facilities of they are ideally suitable for electric grid operating person, electric grid operating person must manage increasing The discrete regenerative resource (such as photovoltaic and wind-driven generator) for being connected to power network of amount.
However, high nominal powers inevitably require big battery (electrode zone planned) be battery operation most High current density, maximum current density by influence the ion charging of electrode and the dynamic (dynamical) factor of exoelectrical reaction and due to Internal drop is limited caused by the internal resistance of cell, and the internal resistance of cell tends to sharply increase at excessively high current density.
When current density increase or when the battery voltage drops, the pressure flow velocity increase of electrolyte solution is increased with passing through Plus the porous mass of the carbon felt of Partial shrinkage flushing and strengthen the reaction power at electrode, although expending more power (Passive Power).
Normally, electrolyte solution enters battery chamber, one or more ingress ports via one or more ingress ports Along general rectangular non-conductive frames or mold backboard non-conductive (unloaded plastics) frame part side distribution, Molding backboard has the core (cell area) as made from mouldable carbon carries conductive aggregation, and electrolyte solution warp Battery chamber, opposite side distribution of one or more outlet ports along non-conductive frames are exited by one or more outlet ports.Pump Auxiliary circulation forces solution via permeable carbon felt electrode, and permeable carbon felt electrode is fully filled whole cell area, Not leave the shunt paths do not blocked by the felt of Partial shrinkage.
Although adding pressure drop, the felt electrode of the Partial shrinkage between ion permeable membrane battery separators and electrical conductance backboard It is required in terms of electrical contact enough in whole cell area is kept, whole cell area can lift the reality of working electrode Matter equipotential, although also other manner attempts the contact provided.
Due to the consideration of electrochemistry and chemical resistance, the influence of numerous different requirements and the selection to can use conductor Strict limitation cause practitioner's (resistant to liquid stream) non-homogeneity intrinsic to incompressible felt in terms of gas permeability, inevitably Preferential flow path is created in porous electrode body material so that partial electrode is in " missing to reduction (or oxidation) ion (starved) " state, causes other parts to be worked under the increased current density of different proportion and thus in unpredictable change Mode under start missing.The excessive pumping of electrolyte solution, in addition to significantly reducing energy efficiency, hardly solves this and asks Topic, and under certain condition possibly even without effect.
These problems can greatly be alleviated by being dramatically reduced the maximum rated current density of battery, but increase battery area The requirement in domain has considerable influence to investment, and this requirement can be such that the selection of oxidation, reduction liquid system does not conform in competition Calculate.
Overcharging for negative electrolyte solutions causes the discharge of hydrogen, and overcharging for positive electrolyte causes the discharge of oxygen, oxygen pair It is damaging in carbon felt electrode, usually used ion permeable membrane prevents the inevitable of the solution substantially circulated in addition Volume and ion are non-equilibrium, and this requires the periodicity releveling of two circuits.
Many instruments have been proposed to provide the information of the condition at carbon felt electrode occurred on electrochemical process, wherein It may mention：
A) by the operating voltage of common potentiometer or the individual battery of equivalent apparatus measures (in bipolar cell pile In the case of there is provided conductive plate in the electronic each battery of voltage probe linear contact lay in special outside).Practice is feasible for test , but because there is the joint risk of corrosion and/or electric leakage using this wiring, it is difficult to compatible in business equipment；
B) common galvanometer or the electric current of the battery via tandem working of equivalent apparatus measures are passed through；
C) typically via the open-circuit voltage of the battery of two kinds of electrolyte solution measurements of circulation in measurement battery；
D) by measuring the probe being immersed in electrolyte solution and being immersed in the reference for being substantially at zero charge state The voltage difference between reference probe in solution, either by the colorimetric analysis of electrolyte solution or passes through conductivity measurement The state of charge of obtained electrolyte solution；
E) solvent in two kinds of different electrolyte solutions and the material of ionic species obtained by chemical analysis is put down The amendment of weighing apparatus.
Up to the present, though maximum dispose the assessment technology of precision instrument and electricity, chemistry and electrochemical parameter, It can influence the generation of charging and discharging process in the battery, can not provide reliable information and go to eliminate the list of many battery piles The adjoint risk of the individual unstable failure of battery, does not observe the decline of overall efficiency yet, less uses and carry beyond any design The intentional increased pumping speed of the liquid flow chamber by different batteries of limitation.These phenomenons are intended to send out more and more It is raw, and when being operated many battery piles deteriorate.
Use bipolar cell pile component the system conventional of commercial operation.This generally hinders the different of monitoring cell voltage Sample or via single battery liquid flow chamber liquid flowing rate difference, many series connection in bipolar cell pile can occur for difference Battery in any one in.Any failure in felt electrode or film level is hardly detectable, and most The failure entirely organized is hindered in the case of number.It is molten that electrolyte is monitored usually using relative complex utensil and to whole bipolar pile The state of charge of liquid, and relative complex utensil can hardly be disposed in single battery rank.
The content of the invention
After designing and testing the very long experience of redox flow battery system, applicants have appreciated that, it was derived from The idea of the measurement of journey parameter, the measurement of procedure parameter in known business system as done, in these procedure parameters Most of usually " average " value for providing relevant parameter, occurs electrochemistry at the carbon felt of any particular battery of battery pile What the condition of process often can not yet reach an agreement so that promote bigger failure.
The equipotential contact of carbon felt electrode is typically concentrated through conductive backings or conductive battery inner panel, phase in many battery piles The surface retained for carbon felt electrode by compression, the uniformity of the mass transfer for the reactive ion species that redox couple is used, The nonideal homogeney of electrical conductivity and permeability, by flow-type electrolyte solution pumping to a frame side from cell area (perimeter side) arrives opposite frame side there is provided any commonly employed aggregation concept, and is assumed to be sometimes useless.
These an open questions perplex the practice of oxidation, reduction liquid storage system, it is found by the applicant that a kind of new many Monopolar cell pile framework and the instrument with special characteristic, these features, which allow operator or electronic controller to gather, to be had The key message of depth and enhanced reliability, " restraining oneself state (state of sufferenance) " is in immediately determine that Any battery, and most it excludes from system and possibly replaces it with idle monopolar cell pile at last.
In a preferred embodiment, the system has classical monopolar cell electrical layout, be based essentially on be connected on it is many Multiple multi-electrode monopolar cell piles between two public DC terminals of battery system；Each multi-electrode monopolar cell pile Positive electrode and negative electrode are collectively coupled to positive outside DC bus (rail) and negative outside DC bus respectively, positive outside DC bus with The electrically coupled in series DC terminals to storage system of negative outside DC bus.
Preferably, each monopolar cell pile has filter-press arrangement, includes the carbon felt of many monopolar cells staggeredly On the positive electrode backboard and negative electrode backboard of electrode, the both sides for being compacted to each electrical conductance backboard, electric current is distributed to felt, except this Two end plates of pile, two end plates distribute electric current to only one felt electrode.Each backboard has what is protruded from liquid flow chamber Handle or handle portion are electrically connected, electrical connection handle or handle portion are connected to each outside DC bus.
It is different from traditional bipolar cell pile configuration, in traditional bipolar cell pile, across any unit cells The reason for voltage of (elementary cell) is because of accident can easily be lifted beyond the limit (for example, for full vanadium oxygen Change reduction liquid fluid system, about 1.6V), crossing this limit water electrolysis can start to become universal, and with electrode breakages The potential risk of the accumulation of oxygen discharge and hydrogen and oxygen in two electrolyte solution circuits, and use monopolar cell electricity Heap is configured, and can effectively prevent above-mentioned risk.Each monopolar cell electricity of the electric current in five monopolar cell piles of series connection Split between five unit cells of heap, and for one group of all five unit cells, cell voltage keep it is constant and It can easily be monitored by external instrument.
The impermeable ion permeable membrane of the liquid that is inserted between two felt electrodes of contrary sign (sign), by one kind The liquid flow chamber of the electrolyte solution of symbol and the liquid flow chamber of the electrolyte solution of contrary sign are separated, by inlet nozzle and going out Mouth nozzle is recycled to and is connected to multiple multi-electrodes and multicell list with surging from each storage tank, inlet nozzle and outlet nozzle Each distribution line of two kinds of electrolyte solutions of pole battery pile.
The flowmeter of each entrance or exit in two kinds of electrolytic liquids, by monitoring in the single company of the pile There is provided the flow via each multi-electrode and multicell monopolar cell pile for the correctness for the electric current split in the electrode backing plate connect Measurement, obtains the information of the abundance on the electrolyte solution liquid stream via each battery gathered indirectly.
The feature being immersed in respectively in flow-type positive electrolyte solution and flow-type negative electrolyte solutions is similar to battery electricity The miniature probe electrode of those features in extremely, each multi-electrode and multicell monopolar cell pile or multicell monopolar cell electricity The entrance of each liquid flow chamber of heap or outlet or there is provided open battery voltage (OCV) measurement preferably at entrance and exit. If although each probe electrode individually with standard (hydrogen) reference electrode coupling infiltrate by identical stream electrolyte solution, The direct measurement of the state of charge of electrolyte solution is provided, state of charge can be assessed relatively expensive without disposing indirectly Standard (hydrogen) reference electrode.
In charging stage and discharge regime at each current capacity, in open-circuit voltage (OCV) and in the company to DC bus There is provided occur in every kind of in two kinds of electrolyte solutions for the voltage difference that measures between total cell voltage (TCV) of the place's of connecing measurement Electrochemical process can not regurgitation factor gross effect measurement.
It is simple, from deployed outside, be coupled to each felt electrode for being assigned electric current according to enhanced monitoring embodiment Or there is provided flow through single felt electrode or flow to be coupled to for the electrical connection handle of each backboard of electrode or the current sensor device of handle The measurement of the electric current of two felt electrodes of the identical backboard of each multi-electrode monopolar cell.According to all electricity more for flowing through series connection The total current of pole monopolar cell pile, divided by unit cells number (few equivalent to the total digital code of backboard 1) and multiply 2 (due to Backboard interlocks to the similar backboard of contrary sign), it can detect and monitor, flow through each felt electrode for being assigned electric current The electric current of any backboard relative to expected value any discrepancy so that final isolate monopole electricity from many stack systems Pond pile simultaneously replaces it with the enable operation of standby unnecessary monopolar cell pile.
Once it is electronic from system and isolate with surging, then it may have shown that any single electrode battery electricity of failure Heap can be disassembled and check, so as to carry out failure cause intervention, can remedy any obstruction or can replace abrasion or The felt electrode and/or the ion permeable membrane of aging damaged by pressure.The multi-electrode monopolar cell pile being refreshed can be then by portion again Reserve battery is affixed one's name in systems or is retained as to be ready for any other battery that substitution is likely to occur problem sooner or later.
In addition, the presence of the probe electrode at the entrance and exit of battery or two kinds of electrolyte solutions of battery pile with And the ability of voltage difference of the measurement between the probe electrode at the entrance and exit of battery or battery pile, it is allowed in charging and During electric discharge, whether each single monopolar cell pile of monitoring occurs in the range of linearity of voltage-state of charge characteristic curve Failure.
The invention of applicant is clearly limited in the accompanying claims, and the content of claim is intended to and the specification Separate, and be incorporated herein by Quick Reference.
Brief description of the drawings
Figure 1A is the electric side on many bipolar cell stack systems of oxidation, reduction liquid according to traditional device configuration Case figure, many bipolar cell stack systems of the oxidation, reduction liquid are illustratively with five of negative terminal different by being connected serially to plus end Bipolar cell pile is constituted.
Figure 1B is the exemplary electrical conceptual scheme of many monopolar cell stack systems of oxidation, reduction liquid on the disclosure, is just pacified Equipment for dress power with Figure 1A can compare, and many monopolar cell stack systems of the oxidation, reduction liquid include being connected serially to plus end The monopole multi-room battery pile different with five of negative terminal.
Fig. 2 is the basic three-dimensional exploded schematic diagram of the multi-room battery pile of example, for the terseness of explanation, with only Three ion permeable membranes (i.e. unit cells) replace five, each monopolar cell pile of Fig. 1 exemplary electrical conceptual scheme Situation also can be such.
Fig. 3 is the details enlarged drawing of Fig. 2 upper part.
Fig. 4 show probe electrode respectively in the entrance or delivery channel of positive electrolyte solution and negative electrolyte solutions and Hydrogen reference electrode, the possibility position in the group upper frame of each monopole multi-room battery of many monopolar cell systems of the disclosure Put.
Fig. 5 shows schematically showing according to the single battery of the disclosure and the voltage of monitoring.
Fig. 6 is the conceptual scheme according to the disclosure, and the program is illustrated how in the charge characteristic curve that can be monitored The range of linearity of voltage-state carries out safety operation.
Fig. 7 shows simple liquid current sensor, and the liquid current sensor can be deployed in many monopolar cell systems of the disclosure Each monopole multi-room battery pile entrance or outlet fluid flow tube in.
Fig. 8 tightens the profile of battery pile for Fig. 2 " press filtration ", shows into the related positive electrode for going out three unit cells The distribution interface of the positive electrolyte solution of liquid flow chamber.
Fig. 9 tightens the profile of three battery piles for Fig. 2 " press filtration ", shows into the related negative electricity for going out three unit cells The distribution interface of the negative electrolyte solutions of pole liquid flow chamber.
Figure 10,11 and 12 are electrochemical potential figure, illustratively show the amount and the limiting threshold value that can set up of measurement with How the punctual intervention of process controller associates.
Embodiment
It is different from the substantive blindness of the operator of the traditional bipolar cell pile device configuration shown in Figure 1A, five Detect, any one in five bipolar cells of series connection can break down occur destructive damage in individual pile, and The downtime of equipment, many monopoles of the disclosure shown in Figure 1B are ultimately resulted in due to the pile survey on implementation to each isolation Battery pile framework, it is allowed to the accurately required substantial amounts of pile and unit required by depth monitoring redox cell system The operating condition of battery.
Figure 1B is the electrical arrangement figure of many monopolar cell stack systems of oxidation, reduction liquid on the disclosure, purely to show The mode (having and the conventional arrangement identical electrical ratings in 1A) of example, the system includes being connected serially to plus end and negative terminal Five different monopole multi-room battery piles.
As symbol is indicated, this is arranged such that the operating voltage to five electrically coupled in series different monopolar cell piles (V1, V2 ... V5), which is monitored, to be possibly realized.In addition, the electric current of five monopole multi-room battery piles except flowing through series connection (illustratively 400A), public current sensor device (CS) (is coupled to five unit electricity of each monopole multi-room battery pile Pond is assigned on the external electrical connections handle of each electrical conductance backboard of the felt electrode of electric current) there is provided on the five of the pile The key message of the uniformity of electric current segmentation between individual unit cells.The connection handle or afterbody of conductive backings constitute suitable electricity Spread sensing resistor, monitor carried on the current sense resistor with to or from each outside DC bus current in proportion electricity Pressure drop.
Fig. 2 is the basic three-dimensional exploded schematic diagram of the multi-room battery pile of example, for the terseness of explanation, with only Three ion permeable membranes (i.e. unit cells) replace five, each monopolar cell pile of Fig. 1 exemplary electrical conceptual scheme Situation also can be such.Fig. 3 is the details enlarged drawing of Fig. 2 upper part.
Electric conductivity backboard 1 must have the electric current of carrying cross section and sufficiently conductive to ensure to ooze into going out porous liquid The equipotential of distribution or the collection of the DC electric current of saturating carbon felt electrode 2, porous liquid permeable carbon felt electrode 2 is attached to leading for backboard 1 Electrical surfaces.Therefore, for the monopolar cell embodiment of consideration, as shown, carbon-based backboard can have metal-cored 1m, gold Category core 1m is fully inserted to the moulding bodies 1a of the electrical conductance aggregation of graphite and/or carbon dust and resin binder inside.Metal Core 1m exposes to have a particular patch (tract) in handle tabs 1t end (just from moulding bodies 1a In the outside of liquid flow chamber, from without being influenceed by common acidic electrolyte solution) so as to be built with DC bus (not shown) Vertical good contact.Can be welding lead along the metal-cored elongated exposed extension of the carbon resin aggregation of molding, It is spaced sufficiently apart in the current flow direction, voltage drop is measured based on the welding lead.
Hydraulic seal around each liquid flow chamber of " press filtration " many battery pile frameworks of considered embodiment, leads to Cross the reverse (counter- being pressed on the impermeable ion permeable membrane separator of the liquid of two liquid flow chambers of each battery Opposed) O-ring is provided.The groove 3g for being suitable for receiving each O-ring is observable in Fig. 3 detailed view.
Section 3s (showing in Fig. 3 detailed view) before channel-shaped framework is glued at handle tabs 1t inside, with And filler rest and reorganization (finishing) recover the continuity of the O-ring groove of the whole surrounding around liquid flow chamber.
In the illustrated embodiment, backboard 1 closely fits in frame 3 (3t) inside, it is contemplated that in backboard Hydraulic seal is not required between corresponding (same-sign) liquid flow chamber on relative face, frame 3 (3t) can be Non-conductive moulded plastic.Key pin 1p and cave (socket) 1s being engaged in the inboard wing of framework makes backboard set and protect Hold in appropriate position.In practice, in many battery pile arrangements of monopole, have from the electric conductivity backboard 1 of external connection There are the distributor or the function of collector of electric current as corresponding carbon felt electrode 2 is entered out, carbon felt electrode 2 passes through the relative of it Face is contacted.
The inner conduit of electrolyte solution is observable in Fig. 3 detailed view, and electrolyte solution is flowed through in backboard 1 Both sides at corresponding (same-sign) electrode chamber.The electrolyte solution being stored in tank via a conduit be pumped with And tank is flow back into via another conduit, in the accompanying drawings, inner conduit 4in and 4out typically extend to whole many battery electricity Pile component, crosses a series of plastic frames, and hydraulic seal is provided by the O-ring being retained in annular groove 4s.
The hole 4h that one be drilled in plastic frame traverses, provides out entering for the liquid flow chamber on the both sides of backboard 1 respectively Mouth interface and discharge coupling.Port holes connect inner conduit with surging, and 4in and 4out belong to considered two of monopolar cell The negative electrolyte solutions of electrode solution flow chamber (the first liquid flow chambers of such as Fig. 2, Fig. 8 and Fig. 9 three battery piles) and positive electrolysis It is any in matter solution, belong to each manifold liquid stream interval 4min (and sightless 4mout in figure 3), 4min is along generally The whole inner side of the framework of rectangle extends.
In practice, flow-type electrolyte solution finds interval 4min into battery, wherein along the backboard 1 of rectangle Side itself (inlet manifold) is allocated, and flow-type liquid finds similar space, wherein in the back of the body of rectangle The relative side of plate 1 is acquired to itself (outlet manifold), in this way, is connect via discharge coupling hole 4h and outlet Mouth 4out discharge batteries.
Through hole ct in the frame is used for the latch of pre-assembled unit, and unit includes single battery, and through hole st is used for The passage of rod (tie rod) is fettered, constraint rod forces together pre- arrangement to form complete many battery piles.
Fig. 4 shows the possible position and alternatively of probe electrode, as shown in the embodiment considered, also shown Go out molten in positive electrolyte respectively in each pile upper frame of each monopole multi-room battery pile of many monopolar cell systems Hydrogen reference electricity in the entry conductor of liquid and negative electrolyte solutions (alternatively, in delivery channel or even in both) The possible position of pole (or other equivalent reference electrodes, such as Ag/AgCl or calomel electrode).What it is according to the disclosure is The key character of system, by their deeper tones can recognize that two measurement to two probe electrodes, with by activated carbon The superficial layer of the fluid permeable of obtained (for example, as made from the identical carbon fiber of activated carbon felt battery electrode 2) infiltration, The superficial layer is binded to conductive carbon-based core conductor (i.e. the connection handle or afterbody of probe electrode) or other carbon-based electrode materials.
Voltage difference between two probe electrodes provides the open-circuit voltage OCV of single monopole multi-room battery pile.In addition, such as By what is be made apparent from the description that follows, only the presence and measurement of probe electrode are molten in each electrolyte of the first symbol The probe electrode in the exit (alternatively in entrance, or even in outlet and entrance) of liquid and the monopolar cell pile of contrary sign Voltage difference between multi-electrode, the indirect but reliable assessment of the state of charge except providing two kinds of electrolyte solutions, also allows Useful information of the derivation on the performance of the ion-permeable membrane separator 5 of felt electrode 2 and single monopole multi-room battery pile.
Certainly, if the probe electrode of activated carbon also has hydrogen or equivalent reference electrode (can by their more shallow tones Identification) be deployed in together in the upper catheter of single monopolar cell pile, then can be by being soaked by identical electrolyte solution Voltage difference between the probe electrode and reference electrode of profit, each electrolyte solution is measured in absolute (direct) mode State of charge.This is possible selection to the multiple direct measurement of the state of electric charge by introducing reference electrode, still, according to The key character of this novel system, substantially equivalent information can be collected in relative (indirect) mode without disposing Required many reference electrodes (be at least each monopolar cell pile and prepare two).
According to the disclosure, represent to Fig. 5 symmetry single monopole multi-room battery pile and monitored electricity electricity is shown Pressure amount.
Difference between pV and OCV represents voltage drop in film and resistance and traversed at electrode by positive electrolyte solution (flowing through) overvoltage (in other words, the effect of the factor of irreversibility be related to the charging stage cathode half-cell and The anodic half-cell of discharge regime)；And the difference between nV and OCV represents the voltage drop through film and resistance and the quilt at electrode (in other words, the effect of the factor of irreversibility is related to the anode half in the charging stage to the overvoltage that negative electrolyte solutions are traversed Battery and the cathode half-cell in discharge regime).
Therefore, by each probe electrode deployment come the amount of measurement pV and nV ability so that distinguish a kind of symbol or Whether the electrode of another symbol is problematic to be possibly realized.
In addition, the difference between the total cell voltage TCV and its open battery voltage OCV of single monopolar cell pile is provided The global measuring of the irreversibility of the charging process and discharge process (under each current capacity) of monocell pile.
As in Figure 5, represented using the symbol of single monopole multi-room battery pile, Fig. 6 illustrates how logical according to the disclosure Cross at the entrance and exit of work unit's battery or monopolar cell pile and dispose probe electrode to monitor in charge characteristic song The range of linearity of voltage-state of line carries out the safety operation of each single monopolar cell pile.
If in the charging stage, monopole multi-room battery pile is in the range of linearity of voltage-state of charge characteristic curve Work, voltage difference delta V- and Δ between the probe electrode that porch and exit are infiltrated by identical electrolyte solution respectively V+ is directly proportional to load and is inversely proportional with the flow velocity of electrolyte.Under constant electric current and liquid stream, as long as battery is maintained at electricity Worked in the range of linearity of voltage-state of lotus indicatrix, these voltage differences (Δ V- and Δ V+) keep constant.
In the negative electrolyte solutions of each battery chamber and positive electrolyte solution are flowed through, if these voltage differences start to become More and more higher, just means that both electrolyte solutions are overcharged, although their state of charge keeps balance.
Differently, if being only that voltage difference in a kind of only electrolyte solution starts rapid raising, and another Voltage difference in electrolyte solution is kept constant or improved with relatively low speed, just means that both electrolyte solutions are uneven Weigh, and promote voltage difference is quick increased a kind of to there is higher state of charge than another.When it happens (and It usually occurs in positive electrolyte solution) and voltage difference delta V+ becomes more and more higher under identical flow velocity, and this is clear and definite Instruction, positive electrolyte solution reached capacity state of charge.This requires two kinds of electrolyte relevelings or pause charging rank Section.
Normally, the releveling of electrolyte solution is shirtsleeve operation, and operation requirement is with the mixing for being coated with Ta-Ir The small film battery of the Ti electrode of oxide, is suitable for oxygen discharge (this shows the overvoltage of the at a fairly low electric discharge of OH+ ions). Therefore, by flowing through the back bias voltage electrode chamber of film battery, positively charged electrolyte solution is reduced.In fact, non-equilibrium Usually by the discharge of the hydrogen in negative electrode or by negative electrolyte oxidation by air, (air can enter contact storage tank Inside) cause.Therefore, releveling is usually only effective to positively charged electrolyte solution, by less film electricity Reduced in the negative electricity pole room in pond by the positively charged electrolyte of fraction, negative electricity pole room passes through cation with positive electrode chamber Exchange membrane is (for example, perfluorinated sulfonic acid, registrar entitling E.I.Du Pont de Nemours) and separate, electrolyte solution can To be only water, so that because water electrolysis method causes oxygen to be separated out on positive Ti electrode.
Each liquid flow chamber of monopolar cell pile is connected to each electrolyte solution circulating line with surging, as shown in Figure 7 The simple liquid current sensor of meaning property description can be deployed in the entrance of each room or outlet fluid flow tube, or as in the accompanying drawings The advised example of the electric pile structure shown, is deployed in the entrance in each monopolar cell pile of the storage system of the disclosure Or in outlet fluid flow tube.Monitoring is provided by the correctness of the liquid stream of two kinds of electrolyte solutions of each multi-room battery pile to be used for Prevent another uncontrolled important information of failure condition.Even if being the deployment liquid stream detection of whole monopole multi-room battery pile Device, is gathered via each single chamber by monitoring the current capacity on each handle or handle portion of each electric conductivity backboard Liquid stream correctness indirect monitoring, for detecting five units in each monopolar cell pile of embodiment described The total current load split between battery it is any non-equilibrium, the reason for its is possible can also be in one of pile liquid flow chamber Obstruction or any liquid stream reduction (except electrode possible failure or be related to experience unit cells degeneration ion permeable membrane Outside).
Fig. 8 tightens the profile of battery pile for Fig. 2 " press filtration ", shows into the related positive electrode for going out three unit cells The distribution port of the positive electrolyte solution of liquid flow chamber.
Fig. 9 tightens the profile of three battery piles for Fig. 2 " press filtration ", shows into the related negative electricity for going out three unit cells The distribution port of the negative electrolyte solutions of pole liquid flow chamber.
Vanadium redox battery system is considered as example, the vanadium of the dissolving comprising same molar ratio is (logical Often in sulfuric acid solution) negative electrolyte solutions and positive electrolyte solution state of charge graphical representation, across by vanadium Three regions limiting of different ionic conditions, figure 10 illustrates corresponding voltage refers to that standard hydrogen joins current potential.
The curve map of Figure 11 copy patterns 10, but indicate to work as when charging stage state of charge (SOC) is about 70% To total cell voltage TCV different contributions when being worked under certain current capacity.According to the disclosure, the voltage of monitoring and half electricity The instruction of the effect of the factor of the irreversibility of pond process (at the negative electrode and positive electrode of monopolar cell pile) is together in song Determined in line chart.
POS-IRRRepresent because voltage is impaired caused by the electricresistance effect in film, Ohmic resistance (this in positive electrode Place is intended for resistance, the combination of the contact resistance and effective resistance of conductive carbon carpet veneer of connection handle or afterbody and backboard) with And the electrochemistry overvoltage (i.e. the positive irreversibility of charging process) of the oxidation of the vanadium dissolved at positive electrode.Similarly, NEG- IRRRepresent because voltage is damaged, the Ohmic resistance in negative electrode (is hereby intended that as connection caused by the electricresistance effect in film Or resistance, the combination of the contact resistance and effective resistance of conductive carbon carpet veneer of afterbody and backboard) and at negative electrode it is molten The electrochemical overvoltage (i.e. the negative sense irreversibility of charging process) of the reduction of the vanadium of solution.
The curve map of Figure 12 copy patterns 10, but indicate to work as when charging stage state of charge (SOC) is about 70% To total cell voltage TCV different contributions when being worked under certain current capacity.According to the disclosure, the voltage of monitoring and half electricity The instruction of the effect of the factor of the irreversibility of pond process (at the negative electrode and positive electrode of monopolar cell pile) is together in song Determined in line chart.
POS-IRRRepresent because voltage is impaired caused by the electricresistance effect in film, Ohmic resistance (this in positive electrode Place is intended for resistance, the combination of the contact resistance and effective resistance of conductive carbon carpet veneer of connection handle or afterbody and backboard) with And the electrochemistry overvoltage (i.e. the positive irreversibility of discharge process) of the reduction of the vanadium dissolved at positive electrode.Similarly, NEG- IRRRepresent because voltage is damaged, the Ohmic resistance in negative electrode (is hereby intended that as connection caused by the electricresistance effect in film The combination of the resistance of shank and backboard, the contact resistance and effective resistance of conductive carbon carpet veneer) and the dissolving at negative electrode Vanadium oxidation electrochemical overvoltage (i.e. the negative sense irreversibility of discharge process).
Such as to those skilled in the art directly it will be evident that the uniformity and redox flow battery system of technological parameter Battery operation real-time conditions instruction (amount instrumentally monitored according to the disclosure), as by Figure 11 described in chart Charging stage and Figure 12 in discharge regime, control algolithm is taught clearly and unambiguously, according to this energy stores The improved control method of system, the value of suitable threshold value is fixed by the amount for various monitorings or algorithm, can therefore be implemented Control algolithm, be arranged on to certain being adapted to property of threshold value other parameters (such as current capacity when charge or discharge with And temperature) function in.
In the breaker being connected with DC bus external electrical, in single monopolar cell pile and switchable bypassed resistor In (being used to the volume of the electrolyte solution to accommodating in the liquid flow chamber of the battery pile disconnected discharge) introduction pipe Magnetic valve by central controller controls, it is allowed to it is electrically separated to show the monopolar cell pile of improper operating condition, and Connect and be coupling in the idle monopolar cell pile of the standby monopolar electrode battery pile of bulk redundancy.Battery except providing failure The replacement of easy and reliable (or even full-automatic) of pile, redundancy can allow to act on charging and discharging process in current capacity Aspect carries out adaptive optimization.
Embodiments described above can be combined to provide further embodiment.Detailed description more than, to reality These and other change can be made by applying example.Generally, in the following claims, the term used should not be construed as will by right Restriction to disclosed specific embodiment in the description, and claim is asked to should be interpreted that including the gamut one with being equal Cause all possible embodiment, these claims have the right exercise its be equal.Correspondingly, claim is not limited by the disclosure System.

Claims (7)

1. a kind of redox flow battery system for energy stores, including：
The different positive electrolyte solution circuits and negative electrolyte solutions circuit of the forced circulation of electrolyte solution, the electrolyte Solution enters out storage tank via each liquid flow chamber of multiple monopolar cell piles, and each described liquid flow chamber is accommodated by liquid not respectively Positive felt electrode and negative felt electrode that permeable ion permeable membrane is separated, the multiple monopolar cell pile in positive DC terminals and Electricity series winding between negative DC terminals, each monopolar cell pile therein or each unit cells have is connected to two kinds with surging The inlet nozzle and outlet nozzle of each distribution line of electrolyte solution, each monopolar cell pile include multiple positive poles staggeredly Backboard and negative pole backboard, each backboard have the electrical connection handle or afterbody protruded from each liquid flow chamber, the electrical connection handle or tail Portion is connected to each outside DC bus, assembles to constitute the monopolar cell pile of multi-electrode multicell, it is characterised in that the system Including：
Feature is similar to the probe electrode of the feature of battery electrode, and the probe electrode is immersed in two kinds of flow-type electrolyte solutions In each in, monopolar cell pile wherein or each entrance of unit cells and/or exit, for measuring work The open-circuit voltage of battery；
The externally measured utensil of total cell voltage of the monopolar cell pile；
Measurement is immersed in the positive pole of the probe electrode and the monopolar cell pile in flow-type negative electrolyte solutions respectively Between backboard, and the probe electrode and the negative pole of the monopolar cell pile being immersed in flow-type positive electrolyte solution The externally measured utensil of two voltage differences between backboard；
The poor externally measured utensil between total cell voltage and described two voltage differences is measured respectively；
The amount of the measurement and the data processing equipment of voltage difference, the data processing equipment are shown in any institute suitable for signalling The exception for stating the threshold limit value in monopolar cell pile exceeds.
2. redox flow battery system according to claim 1, wherein probe electrode are immersed in described two flowings In each in formula electrolyte solution, entering out each liquid flow chamber of monopolar cell pile therein or each unit cells Porch and exit；
The redox flow battery system also includes being soaked by electrolyte solution of the same race in porch and exit measurement respectively The externally measured utensil of voltage difference between the probe electrode of profit, using the additional input as the data processing equipment.
3. redox flow battery system according to claim 1, further comprises the electricity of each conductive backings Current sensor device in connection handle or afterbody, the current sensor device is suitable to each battery of the monitoring in monopolar cell pile The electric current flowed in electrode, extraly to input these current measurement results to the data processing equipment.
4. redox flow battery system according to claim 1, further comprises through two kinds of different electrolyte The liquid current sensor of each liquid flow chamber of solution, the state of the liquid current sensor is extraly inputted to data processing dress Put.
5. a kind of method for the operation for controlling the redox flow battery system for energy stores, the oxidation, reduction liquid Battery system includes：The different positive electrolyte solution loop of the forced circulation of electrolyte solution and negative electrolyte solutions loop, The electrolyte solution enters out storage tank via each liquid flow chamber of multiple monopolar cell piles, and each described liquid flow chamber is held respectively Receive the positive felt electrode and negative felt electrode separated by the impermeable ion permeable membrane of liquid, the multiple monopolar cell pile exists Electricity series winding just between DC terminals and negative DC terminals, each monopolar cell pile therein or each unit cells, which have, surges ground The inlet nozzle and outlet nozzle of each distribution line of two kinds of electrolyte solutions are connected to, each monopolar cell pile is included staggeredly Multiple positive pole backboards and negative pole backboard, each backboard have from each liquid flow chamber protrude electrical connection handle or afterbody, the electricity Connection handle or afterbody are connected to each outside DC bus, assemble to constitute the monopolar cell pile of multi-electrode multicell, methods described Including step：
The probe electrode that the feature of battery electrode is similar to by feature measures the open-circuit voltage of working battery, the probe electrode It is immersed in each in two kinds of flow-type electrolyte solutions, each of monopolar cell pile wherein or unit cells enter Mouth and/or exit；
Measure total cell voltage of work monopolar cell pile；
Measurement is immersed in the positive pole backboard of the probe electrode and monopolar cell pile in flow-type negative electrolyte solutions respectively Between and the probe electrode and the negative pole backboard of the monopolar cell pile that are immersed in flow-type positive electrolyte solution Between two voltage differences；
The difference between total cell voltage and described two voltage differences is measured respectively；
Handle the amount and voltage difference of measurement and signal and show that the exception of preset threshold threshold value exceeds.
6. the method for the operation according to claim 5 for controlling the redox flow battery system for energy stores, Wherein probe electrode be immersed in described two flow-type electrolyte solutions each in, entering out monopolar cell pile therein Or the porch and exit of each liquid flow chamber of each unit cells, methods described further comprises step：
Voltage between the externally measured probe electrode infiltrated by electrolyte solution of the same race in porch and exit respectively Difference；
The increase of the voltage difference of measurement is monitored, the increase, which is represented, reaches the limit of state of charge, and two kinds of different electricity of monitoring The difference of the increment rate of electrolyte solution, the difference represents the imbalance of their state of charge.
7. side of the control for the operation of the redox flow battery system of energy stores according to claim 5 or 6 Method, further comprises step：
The electric current flowed in each battery electrode of monopolar cell pile, the current sense are measured using current sensor device Device is coupled to the electrical connection handle or afterbody of each conductive backings；
The difference between the voltage difference of measurement is monitored, the difference represents one or more units electricity of the monopolar cell pile The change of the performance in pond.
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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITBO20130327A1 (en) * 2013-06-25 2014-12-26 Proxhima S R L FLOW BATTERY
DE112014005149B4 (en) * 2013-11-21 2021-08-05 Robert Bosch Gmbh System and method for minimizing transportation-related loss of performance in a flow battery system
TWI509870B (en) * 2014-07-18 2015-11-21 Inst Nuclear Energy Res Atomic Energy Council Method of Charging and Discharging Power by Using Electrolyte Fluid Lines
KR101824170B1 (en) * 2016-09-30 2018-01-31 롯데케미칼 주식회사 Redox flow battery
US11264631B2 (en) * 2018-08-10 2022-03-01 Ess Tech, Inc. Methods and system for manufacturing a redox flow battery system by roll-to-roll processing
JP2020068145A (en) * 2018-10-25 2020-04-30 三菱自動車工業株式会社 Control apparatus of redox flow cell
US11081712B2 (en) 2018-10-26 2021-08-03 Saudi Arabian Oil Company Method and system to modify the performance of a redox flow battery
CA3148813A1 (en) * 2019-08-02 2021-02-11 Invinity Energy Systems (Canada) Corporation Redox flow battery arrays and methods for state of charge balancing
TWI726516B (en) * 2019-12-04 2021-05-01 財團法人工業技術研究院 Flow battery system and control method of the same
CN113270624B (en) * 2021-04-14 2022-03-22 上海交通大学 Flow battery subsystem with catalyst management and electrolyte capacity rebalancing
CA3233158A1 (en) * 2021-11-10 2023-05-19 Rebecca Nicole SEGEL Measuring electro-chemical properties of flowable materials
WO2024056281A1 (en) * 2022-09-16 2024-03-21 Voith Patent Gmbh Redox flow battery and method for operating same
JP7390090B1 (en) * 2023-05-17 2023-12-01 ｉｎｅｏｖａ株式会社 flow battery
CN117317307B (en) * 2023-11-30 2024-03-22 湖南省银峰新能源有限公司 Liquid flow regulating method and device for energy storage system of all-vanadium redox flow battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1284208A (en) * 1998-01-28 2001-02-14 凯米科有限责任公司 Rebox flow battery system and cell stack
CN1605150A (en) * 2001-11-16 2005-04-06 斯奎勒尔控股有限公司 Oxidation reduction reflux battery system and its operation method
CN1765027A (en) * 2003-03-04 2006-04-26 斯奎勒尔控股有限公司 Multi voltage tap oxidation-reduction fluid flow battery packs composed by stack battery assembly capable of adjusting battery area

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1212303B (en) 1978-07-10 1989-11-22 Elche Ltd REDOX ACCUMULATOR.
US4786567A (en) 1986-02-11 1988-11-22 Unisearch Limited All-vanadium redox battery
WO1990003666A1 (en) * 1988-09-23 1990-04-05 Unisearch Limited State of charge of redox cell
JP3193990B2 (en) * 1993-12-24 2001-07-30 経済産業省産業技術総合研究所長 Electrolyte flow battery
JP3193991B2 (en) 1993-12-24 2001-07-30 経済産業省産業技術総合研究所長 Electrolyte flow battery
TR200100534T1 (en) 1999-07-01 2001-08-21 Squirrel Holdings Ltd Bipolar electro-chemical reactor, separated by membrane
KR20010106464A (en) 1999-07-01 2001-11-29 추후제출 Bipolar electrode for electrochemical redox reactions
DK1186069T3 (en) 2000-03-31 2003-10-27 Squirrel Holdings Ltd Redox flow-through battery and method for operating it
KR20030034146A (en) 2000-08-16 2003-05-01 스쿼럴 홀딩스 리미티드 Vanadium electrolyte preparation using asymmetric vanadium reduction cells and use of an asymmetric vanadium reduction cell for rebalancing the state of charge of the electrolytes of an operating vanadium redox battery
ITVA20010019A1 (en) 2001-06-28 2002-12-28 Chemieco S R L REDOX CELL WITH NON-SELECTIVE IONIC SEPARATOR
ITVA20010022A1 (en) 2001-07-11 2003-01-11 Chemieco Srl STATIC VOLTAGE INVERTER FOR BATTERY SYSTEM
JP2006114360A (en) * 2004-10-14 2006-04-27 Kansai Electric Power Co Inc:The Method for operating redox flow battery system
US8158277B1 (en) * 2010-09-30 2012-04-17 Global Energy Science, LLC (California) Cross-flow electrochemical batteries
WO2012001446A1 (en) 2010-06-29 2012-01-05 Krisada Kampanatsanyakorn Compact frameless bipolar stack for a multicell electrochemical reactor with planar bipolar electrical interconnects and internal ducting of circulation of electrolyte solutions through all respective cell compartments
CN103181014A (en) 2010-08-13 2013-06-26 斯奎勒尔控股有限公司 Redox flow battery system employing different charge and discharge cells
WO2012032368A1 (en) 2010-09-07 2012-03-15 Krisada Kampanatsanyakorn Multi-tier redox flow cell stack of monopolar cells with juxtaposed sideway extended bipolar intercell interconnects on every tier of the stack
WO2012042288A1 (en) 2010-10-01 2012-04-05 Krisada Kampanatsanyakorn Frameless electrochemical cell stack having self centering rigid plastic bushings in aligned through holes of interconnects and membrane assemblies
AT510723B1 (en) 2010-12-21 2012-06-15 Cellstrom Gmbh FRAME OF A CELL OF A REDOX FLOW BATTERY
US8980484B2 (en) * 2011-03-29 2015-03-17 Enervault Corporation Monitoring electrolyte concentrations in redox flow battery systems
WO2014039731A1 (en) * 2012-09-05 2014-03-13 Energy Storage Systems, Inc. Redox and plating electrode systems for an all-iron hybrid flow battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1284208A (en) * 1998-01-28 2001-02-14 凯米科有限责任公司 Rebox flow battery system and cell stack
CN1605150A (en) * 2001-11-16 2005-04-06 斯奎勒尔控股有限公司 Oxidation reduction reflux battery system and its operation method
CN1765027A (en) * 2003-03-04 2006-04-26 斯奎勒尔控股有限公司 Multi voltage tap oxidation-reduction fluid flow battery packs composed by stack battery assembly capable of adjusting battery area

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